Spurious Oscillations Caused by Density Functional Approximations: Who is to Blame? Exchange or Correlation?

ABSTRACT: We analyze the varying susceptibilities of different density functional approximations (DFAs) to present spurious oscillations on the profiles of several vibrational properties. Among other problems, these spurious oscillations cause significant errors in harmonic and anharmonic IR and Raman frequencies and intensities. This work hinges on a judicious strategy to dissect the exchange and correlation components of DFAs and pinpoint the origins of these oscillations. We identify spurious oscillations in derivatives of all energy components with respect to nuclear displacements, including those energy terms that do not involve numerical integrations. These indirect spurious oscillations are attributed to suboptimal electron densities resulting from a self-consistent field procedure usi

SUBMITTER: Sitkiewicz SP 

PROVIDER: S-EPMC11044272 | biostudies-literature | 2024 Apr

REPOSITORIES: biostudies-literature